Mineral oil composition



Patented Feb, 20, 1945 2,369,008 MINERAL on. comrosmou Rush F. McClcary, Beacon, N. I, assigns:- to The Texas Company, New York, N. Y., a corporatlon of Delaware .No Drawing. Application November 29, 1941. Serial No. 421.041

12 Claims.

This invention relates to an improved lubricating oil adapted for use in internal combustion engines and particularly to lubricating oil having a combination of additive ingredients incorporated therein.

It is generally recognized that in the recent development of internal combustion engines, and

.bus and tractor service where the piston temperatures range from approximately 425 F. to 650 F. and pressures from the oxidizing combustion gases are as high as 750 to 1150 pounds per square inch, have seriously accentuated such problems of corrosion, oxidation and varnish and lacquer formation in the refined mineral lubricating oils withthe resultant deleterious eflect on the eiflciency of the engines. The nature and extent of these problems depend upon the conditions of operation of the'particular engine type and upon the type and extent .of refining of the base oil used, and numerous other factors.

The tendency of mineral lubricating oils to deposit carbonaceous materials which are commonly referred to as varnish and lacquer deposits aboutthe valves, rings, pistons, cylinders and other engine parts, can be largely overcome by the addition of certain types of additive ingred ients which possess detergent qualities when dissolved or dispersed in lubricating oils. By detergent properties is meant not only that property which aids in dispersing, removing or purging foreign materials which accumulate on the sur-' face of the engine parts, but also that property which prevents the accumulation or deposition of such materials, as distinguished from solvent action upon the accumulations or deposits.

In addition thereto, the tendency of these oils to become oxidized and to corrode the metal surfaces with which the lubricating oil comes in contact may be, overcome or reduced by the addition of additive components which possess antioxidant and/or anti-corrosive properties when dissolved or. dispersed in mineral lubricating oils.

the body of the oil and etl'ect a reduction or elimination of weight loss of the lubricated surfaces, particularly bearing surfaces. 7

It is the object of the prwent invention to provide a mineral oil composition possessing combined detergent, anti-oxidant and anti-corrosive properties by incorporating in a mineral lubricating oil an additive ingredient possessing predominant detergent properties with an additive ingredient possessing predominant anti-oxidant and anti-corrosive properties.

According to the present invention, a class of compounds has been found which when incorporated in a mineral lubricating oil possess exceptional detergent properties.

These compounds may be broadly described as oil-soluble alicycloxy aliphatic alcohols, ether alcohols and their corresponding metal alcoholates. These compounds possess an alicyclic or cycloaliphatic nucleus bound to an aliphatic alcohol radical through an ether linkage. The allphatic alcohol radical may be subdivided by ether linkages into similar or dissimilar aliphatic radicals and the alcohol radical may be retained as such or in the form of its corresponding metal alcoholates.

When describing the compounds of the present invention throughout the specification and claims, it is. to be understood that when reference is made to an ether linkage or an alcohol or an alcoholate radical, the corresponding thio ethers, thio alcohols and thio alcoholates are meant to be included. This class of compounds may be illustrated by the following structural formula I v-C (XRiY) r in which C is a cycloaliphatic nucleus: B may be a hydrogen, alkyl, aryl, aralkyl, cycloallwl or naphthenyl radical together with substituted derivatives thereof: R1 is an aliphatic radical which may contain oxygen or sulfur substituents or both in the form of ether and thio ether linkages together with further substituents in the form of halogen, oxygen, sulfur, or nitrogen derivatives; X may be either oxygen or sulfur; Y may be an hydroxyl radical (OH). a sulfhydryl radical (SH) or metal salts thereof; and 1! and z are integers of one or more. The cycloaliphatic nucleus designated by C in the formula includes cycloaliphatic radicals containing one or more cyclic nuclei together with hydrogenated aromatic radicals possessing varying degrees of hydro- These anti-oxidant or anti-corrosive properties are meant to include all such properties which eitect a'reductlon of the oxidation products in genation. The monocyclic nuclei may be derived from such cycloaliphatic compounds as cyclopentame, cyclohexane, cycloheptane, cyclooctane etc.

together with their substituted derivatives. The polycyclic nuclei may be derived from such compounds as bicyclohexane, bicyclooctane, decahydronaphthalene and the compounds obtained from petroleum oil, usually referred to as naphthenes, which consist of alkylated cycloaliphatic compounds containing one or more cyclic nuclei. Within this classification are also included such radicals as may be derived from the camphanes and sterols such as bomeol and cholesterol. Further, these cycloaliphatic nuclei may be derived from the monoor polycycloalkenes or cycloalkadienes as, for example, cyclohexene and cyclohexadiene. The metal derivatives of this class of compounds which are formed by the substiution of the replaceable hydrogen in the hydroxyl radical (OH), or'the sulfhydryl radical (SH), include any of the following meals: sodium. potassium. lithium. calcium, barium, strontium, tin, chromium, cobalt, magnesium, manganese, zinc, nickel, aluminum and copper.

One of the preferred types of compounds within the scope of the present invention may be illustrated by the following structural formula in which C, R, X, Y, 1; and 2 follow the same classification as given in the foregoing Formula I and in which R: is an aliphatic radical containing up to 5 carbon atoms, and 11. may be zero or an integer from 1 to 5. B: may also contain oxygen. halogen, sulfur, and nitrogen derivatives which do not aflect the oil-solubility of the compound. Among these derivatives may be mentioned the hydroiw, halogenated. sulfurized, mercapto and amino derivatives.

The constituent R as present in both Formulas I and II is preferably a radical which is used to impart oil-solubility to the compounds. However. as the aliphatic radicals R1 and R: increase in length, thereby in themselves increasing the oilsolubility, the eflect of R may be diminished and may be present as hydrogen or a condensed aromatic nucleus. Especially is this true when more than one aliphatic ether-alcohol constituent is present in the ring system. Derivatives of It may further be used to impart additional improving properties to the mineral oil composition such as chlorinated derivatives to improve the load carrying qualities and sulfurized derivatives to enhance the anti-corrosive properties. As examples of the type of substituted derivatives of R which lie within the scope of the present invention may be mentioned such radicals as the following: un-

saturated alkyl; sulfurized alkyi, aralkyl, cycloalkyl, and naphthenyl; mercapto alkyl, aralkyl. cycioaikyl and naphthenyl: acyl; ,aryloxy, aralkoxy and cycioalkoxy; halogenated eikyi, aryl, aralkyi. cycloalkyl and naphthenyl; hydroxy alkyl, aryl, aralkyl. cycloalkyl and naphthenyl;

amino alkyl, aryl, aralkyl. cycloalkyl and naphthenyl: etc. These hydrocarbon radicals and their derivatives may be obtained from such sources as petroleum wax, gasoline polymers, kerosine fractions, petroleum naphthenates, lon chain alcohols. naturally occurring waxes, coal tar fractions. solvent refining extracts, etc. As shown in Formulas I and II, the substituent B may be present in one or more positions in the cycloaliphatic nucleus. The number of positions which may be substituted by R is dependent upon the number of free nuclear hydrogens resent and the particular properties desired from the compound.

It is to be understood that the fundamental groups present in the radicals --XR1Y and --X-(RzX)-R:Y are the ether or thio ether radical X and the hydroxyl or sulfhydryl radical Y. R1, in the Formula I, may or may not contain further ether and/or thio ether linkages whereas R2 in Formula II is fundamentally a hydrocarbon radical containing up to 5 carbon atoms. The hydroxyl or sulfhydryl radical Y may be retained as such or converted to its metal salt which may consist of any of the above mentioned metals and preferably the salts of the alkaline earth metals.

In order to illustrate the types of aliphatic radicals within the scope of the classification of R1 and their association with X and Y in the radical --XR1Y 0! Formula I, the following simple radicals are presented:

As previously mentioned the aliphatic substituent Rs in Formula II isbasicaily a hydrocarbon radical containing up to 5 carbon atoms.

However. Re may contain further subetituents.

EXALIPLEI A mixture of 450 grams of 2-4 diamyl cyclohexanol, 45 grams of sodium, 1000 cc. benzene and 50 cc. alcohol, were stirred together until the sodium was dissolved. To the resulting solution. 175 grams of ethylene chlorohydrin was added during a period of two hours. During this addition, C. after which thereaction mass was heated to '75-80 C. for approximately two hours. The resulting salt was filtered out and the solvent and excess ethylene chlorohydrin were removed by distillation in vacuo. The residual oily liquid which consisted of diamyl cyclohexoxy ethanol weighed 440 grams and had a hydroxyl number EXAMPLE II Four hundred grams of diamyl cyclohexoxy ethanol prepared in accordance with Example I was added to a solution of 400 grams of calcium dissolved in 1000 cc. of liquid ammonia with substantial agitation. Two liters of toluene were added and the ammonia evaporated oil. The toluene solution of calcium diamyl cyclohexoxy ethylate was warmed and filtered. The toluene was removed by distillation in vacuo and the calcium salt dissolved in an equal weight of lubricating oil to give a 50% concentrate.

It is to be understood that in place of the diamyl cyclohexanolused in Example I, other substituted or unsubstituted cycloaliphatic compounds may be used and that in place of the alcohol, other aliphatic alcohol; or mercaptans may be used. Further, the calcium of Example 11 may be substituted by any of the other metals previously mentioned.

In accordance with the object of the present invention, a mineral oil compodtion possessing combined detergent. anti-oxidant. and anti-corrosive properties is obtained by combining the foregoing detergent additive component with an oil-solubl additive component possessing antioxidant and anti-concave p perties.

Ithasbeenl' inpreparingailuished lubricant that it is usually necessary to provide mineral oil composition possessin both detergent and anti-corrosive properties. The relative amounts of these component factors which are necessary in a lubricant depend upon the particular service and operating conditions involved. The antioxithe temperature was maintained at 35 to 50 the test the oil was continuously matic sulfur compounds such as aromatic sulfldes and aromatic thio ethers, etc. As specific examples of these anti-corrosive compounds may be mentioned tri (dimethylaminomethyl) phenol, amylthiomethyl octyl phenol, di (amylthiomethyl) phenol, polymerphenol disumde, sulfurized wax, sulfurized ethyl oleate, sulfurized terpinolene, suliurized sperm oil and cresyl thiophosphite.

As previously mentioned, the range or proportions of the individual additive components when used in combination vary with the particular service and operating conditions involved. It is therefore desirable to set forth the limits and preferred ranges of these components in four of the more common uses.

Detergent Anti-corrosive Preferred Preferred Limits "use Limits mm Motor oils 0.1-1.5 0.1-0. 5 0.1-3. 5 d 14.0 Diesel oils and heavy duty motor oils. 0. l-3. 0. 254. 0 0. l-5. 0 0. -6. 0 Airplane oils. 0.1-2.0 0. -1. 0 a 1-5. 0 o 5-2.0 Turbine oils 0 cm. 5 a 01-0. 1 0. 01-2. 0 a 01-0. 2

In order to illustrate the improving qalities or the aforementioned combinations in a mineral lubricating oil, the results of the following empirical test are presented. This test consists of a course structure copper-lead bearing specimen encased in a special non-wear bushing rotatably mounted on a stainless steel shaft and immersed in a glass pot of the oil to be tested. The tested oil was heated to a controlled temperature of either 250 F. or 350 F. and continuously circulated between the bearing specimen and the shaft for 10 hours. Throughout aa'itated by means of copper bodies which acted as oxidation accelerators. The bearing specimen was weighed before the test and after the 10-hour period, and the loss of weight recorded in milligrams. The reference oil of this test was a mixed base solvent-refined dewaxed Mid-Continent lubricating oil of an 8. A. E. srade. To the reference oil of the combination of additives of the present invention using calcium diamylcyclohexoxycthylate as the reference detergcnt'component. The results of two runs at both 250' I". and 850' 1".

are presented: W

Basanm Connosron-Corrn-Lup (Tm Home) Loss of weight in mg.

no I any I.

orenoe oil H sic-a1 Oil A (reissues oil plus 0.5% calcium diarnylcyclones ylstc) H 373-37 Oil aplul 2. nmylthiomethyi octylphenoli. i-l Oil l. tI'Kdimethy aminomethyl) H; 1H 0 A plus 'iIiifiil'riH lihiomethyl) new I; m-as OilAplus 1.5% sullurlodwax 3- 1 lac-m on A plus egg, sullurired ethyl 01m. 0-1 11-0: 011A plus I. saliurised terpiuolme. 0-0 H on A flux 3.0% suliuriwl 8 oil. o-i 42-80 on A plus 1.5% cresyl tl'iior a 0-1 Illoillngluplus 1.5% henryl d ethy dithlooarba- H on A k" use; bolh'sibiieifiiiiiififldiifi o-o sic-m u n Obviously many modifications and variation;

was added varyin 'proportlons ing anti corrosive properties,

4 tions should be imposed as are indicated in the appended claims.

I claim:

l. A lubricant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula E e-(X31108 ing oil having incorporated therein (Ll-3.0% by weight of an oil-soluble compound of the following general formula R C-(KEN): in which is a cycloaliphatic radical, R is a radical from thegroup consisting of a hydrogen,

alkyl, aryl, aralkyl, cycloalkyl and naphthenyl radicals, R1 is an aliphatic radical, X is an element from the group consisting of oxygen and sulfur, Y is a radical selected from the group consisting of hydroxyl sulfhydryl radicals and metal salts thereof, and-y and z are integers of at least one; and 0.1-5.0% by weight of an oilsoluble additive ingredient possessing anti-corrosive P p rties. g

3.- A lubricant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula in which C is a cycloaliphatic radical, R is a radfrom the group consisting of hydroali thenyl radicals, R: is an aliphatic radical contaming from 1 to 5 carbon atoms. X is an elementselected from the group consisting of oxygen and sulfur, Y is a radical selected from the group consisting of hydroxyl and sulfhydryl radicals and metal salts thereof, 11 and z are integers of at least one, and n is a numeral selected from the group consisting of oil-soluble additive component possessing anticorrosive properties. I

4. Alubrlcant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula:

R C-(mil): I a

in which C is a cycloaliphatic radical. R is a-radlcal from the group c of hydrog Bi is an aliphatic radical, X-is an element from the group consisting of oxygen and sulfur. Y is a radical selected from the group consisting of hydroxyl and sulfhydryl radicals and metal salts thereof, and p and c are integers of at least one; and an oil-soluble'addltive component, possessselected from the group consisting of organic esters of sulfur-containing phosphorus acids. sinfurised esters of fatty acidasulfurined. wax compoimds, suifuriaed terpenes, aromatic thicaryl, aralkyl, cycloalkyl and naph 0,1,2,3,4and5;andan sulfurlzed fatty olls,-

asoaaos ethers, aromatic sulfides, and sulfur-containin carbamic acid derivatives.

5. A lubricant comprising a mineral lubricating oil and a minor proportion of the combination of an oil-soluble compound selected from the group consisting of alicycloxy aliphatic alcohols and their corresponding metal alcoholates and an oil-soluble additive ingredient possesslng anti-oxidant and anti-corrosive properties;

6. A l bricant comprising a major proportion of a mineral lubricating oil and a minor proportion of the combination of an oil-soluble compound selected from the group consisting of alicycloxy aliphatic alcohols and their corresponding metal alcoholates, and an oil-soluble sulfurcontaining compound possessing anti-corrosive properties.

'7. A lubricant comprising a mineral lubricating oil having incorporated therein 0.l-3.0% by weight of an oil-soluble compound selected from the group consisting of alicycloxy aliphatic alcohols and their corresponding metal alcoholates, and OBI-5.0% by weight of an oil-soluble additive component possessing anti-oxidant and anti-corrosive properties.

8. A lubricant comprising a major proportion of a mineral lubricating oil, a minor proportion of the combination of an oil-soluble compound selected from the group consisting of alicycloxy aliphatic alcohols and their corresponding metal alcoholates, and an oil-soluble compound possessing anti-corrosive properties selected from the group consisting of organic esters of sulfurcontaining phosphorus acids, sulfurized fatty oils, sulfurized esters of fatty acids, sulfurized wax compounds, sulfurized terpenes, aromatic thioethers, aromatic sulfides, and sulfur-containing carbamic acid derivatives.

9. A lubricant comprising a mineral lubricating oil having incorporated therein a small amount of the combination of an oil-soluble metal alicycloxy aliphatic alcoholate, and an oilsoluble ingredient possessing anti-corrosive properties.

10. A lubricant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula:

in which 0 is a cycloaliphatic radical, R is a radicai selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl and naphthenyl radicals, R, is an aliphatic radical containing from 1 to 5 carbon atoms, K is an element selected from the group consisting of oxy- 9 aryl, aralkyl, cycloalkyland naphthenyi radicals,

gen and sulfur, Y is an alkaline earth metal oxide, u and z are integers of at least one, and n is a numeral selected from the group consisting of 0, 1, 2, 3, 4 and 5; and an oil-soluble sulfurized composition possessing anti-corrosive properties.

11. A lubricant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula:

in which C is a cycloaliphatic radical, R. is a radide, 1! and z are integers of at least one, and n is a numeral selected from the group consisting oi 0, 1, 2, 3, 4 and 5; and an oil-soluble sulfurcontaining carbamic acid derivative possessing anti-corrosive properties.

12. A lubricant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula:

R -C-(X-(IhX) i-mm in which C is a cycloaliphatic radical, R is a rad- CER'I'IFICAIE 0F CORRECTION.

Patent No. 2,369, 908- RUSH F McCIEARY.

0nd column, line 1718, strike on page 5, second column,

Signed and sealed fliis (Seal) February 20, 19Li5.

: Page 1, sectthe comma andwords ether alcohols"- line 28, for "qalities" v i first column, line 2, claim 2, after that the said Letters Patent should be read with read --qualities--; "hydroxyl" insert --and--;

and this correction therese in the Patent:

5th day of June, A. n. 1915.

Leslie Frazer Acting Commissioner of Patents.

ide, 1! and z are integers of at least one, and n is a numeral selected from the group consisting oi 0, 1, 2, 3, 4 and 5; and an oil-soluble sulfurcontaining carbamic acid derivative possessing anti-corrosive properties.

12. A lubricant comprising a major proportion of a mineral lubricating oil and a minor proportion of a combination of an oil-soluble compound of the following general formula:

R -C-(X-(IhX) i-mm in which C is a cycloaliphatic radical, R is a rad- CER'I'IFICAIE 0F CORRECTION.

Patent No. 2,369, 908- RUSH F McCIEARY.

0nd column, line 1718, strike on page 5, second column,

Signed and sealed fliis (Seal) February 20, 19Li5.

: Page 1, sectthe comma andwords ether alcohols"- line 28, for "qalities" v i first column, line 2, claim 2, after that the said Letters Patent should be read with read --qualities--; "hydroxyl" insert --and--;

and this correction therese in the Patent:

5th day of June, A. n. 1915.

Leslie Frazer Acting Commissioner of Patents. 

